Formal [4+2] cycloaddition of 3-phenylcyclobutanones with nitriles

Various 3-phenylcyclobutanones reacted with aliphatic and aromatic nitriles in the presence of Me₃SiOTf to afford dihydropyridones by formal [4+2] cycloaddition.     

Co-cross-linking of bio-based multi-functional epoxide and bisphenol A diglycidyl ether with 2-ethyl-4-methylimidazole

A co-cross-linking reaction of bio-based multi-functional epoxides (1) derived from limonene oxide and bisphenol A diglycidyl ether (BPADE) in the presence of 2-ethyl-4-methylimidazole (EMI) as a cross-linker afforded the corresponding network copolymers (2) having the 10% thermal decomposition temperature (T_d10) of 294.4?°C at maximum. Adhesive strength induced by 1, especially tetra-functional epoxide, and BPADE exhibited remarkably higher than that by BPADE alone.     

Synthesis of (Z)-β-(Carbonylamino)alkenylindium through Regioselective anti-Carboindation of Ynamides and Its Transformation to Multisubstituted Enamides

The regioselective anti-carboindation of ynamides by using InBr₃ and silylated nucleophiles was developed to synthesize (Z)-β-(carbonylamino)alkenylindiums. The X-ray crystallographic analysis of an alkenylindium suggested that the reaction proceeded in an anti-addition fashion. In contrast to reported syn-carbometalations of ynamides by using organometallics, a cooperation of InBr₃ and silylated nucleophiles to ynamides achieved an anti-addition, which was supported by DFT calculations. The scope of substrates included various ynamides and silylated nucleophiles, such as silyl ketene acetals and silyl ketene imines. The transformation of synthesized alkenylindiums by iodination, radical coupling, and Pd-catalyzed cross-coupling successfully afforded trisubstituted enamines with high regio- and stereoselectivities.     

Toward numerical simulations of fluid–structure interactions for investigation of obstructive sleep apnea

Obstructive sleep apnea (OSA) is a medical condition characterized by repetitive partial or complete occlusion of the airway during sleep. The soft tissues in the airway of OSA patients are prone to collapse under the low-pressure loads incurred during breathing. This paper describes efforts toward the development of a numerical tool for simulation of air–tissue interactions in the upper airway of patients with sleep apnea. A procedure by which patient-specific airway geometries are segmented and processed from dental cone-beam CT scans into signed distance fields is presented. A sharp-interface embedded boundary method based on the signed distance field is used on Cartesian grids for resolving the airflow in the airway geometries. For simulation of structure mechanics with large expected displacements, a cut-cell finite element method with nonlinear Green strains is used. The fluid and structure solvers are strongly coupled with a partitioned iterative algorithm. Preliminary results are shown for flow simulation inside the three-dimensional rigid upper airway of patients with obstructive sleep apnea. Two validation cases for the fluid–structure coupling problem are also presented.     

Vinyl Polymerization. 431. Vinyl Polymerizations Initiated by Block and Random Poly(Styrene-co-Sodium Methacrylate)

Abstract

The polymerization of some kinds of vinyl monomer was found to occur without an ordinary initiator in aqueous solutions of AB-type block or random copolymers of sodium methacrylate with styrene as a so-called “uncatalyzed polymerization.” Although the spin trapping technique showed that the initiation mechanism by the block copolymer was the same as that by the random copolymer, the initiating ability of the block copolymer was lower than that of the random copolymer. Such results are attributable to the difference in the incorporating ability of monomer into the micelles formed by the block copolymer and into the hydrophobic areas formed by the random copolymer.